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Acta Cryst. (2007). E63, m1837    [ doi:10.1107/S1600536807025342 ]

Acetonitrile{2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato-[kappa]3N,N',O}(thiocyanato-[kappa]N)copper(II)

L.-J. Ye and Z. . You

Abstract top

In the title mononuclear copper(II) complex, [Cu(C12H16N3O3)(NCS)(C2H3N)], the CuII atom is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff-base ligand and one N atom of the thiocyanate ligand defining the basal plane. The apical position is occupied by the N atom of the acetonitrile molecule. The structure is stabilized by intramolecular C-H...N and intermolecular C-H...O hydrogen-bonding interactions.

Comment top

Recently, we have reported a thiocyanate coordinated zinc(II) complex (Ye & You, 2007). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title compound, (I).

The CuII atom in (I) is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff base ligand and one N atom of the thiocyanate ligand defining the basal plane, and the N atom of the acetonitrile group occupying the apical position (Fig. 1). Selected bond distances and angles within the coordination sphere of the metal are given in Table 1. The molecular and crystal structures are stabilized by C—H···N and C—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Ye & You (2007); Hu et al. (2005).

Experimental top

5-Nitrosalicylaldehyde (0.1 mmol, 16.5 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg), and copper acetate monohydrate (0.1 mmol, 20.0 mg) were dissolved in an acetonitrile solution (10 ml). The mixture was stirred at room temperature for 10 min, giving a clear blue solution. Crystals of the title compound were formed by slow evaporation of the solvent over a week at room temperature.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C–H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, shown with 30% probability displacement ellipsoids.
Acetonitrile{2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato- κ3N,N',O}(thiocyanato-κN)copper(II) top
Crystal data top
[Cu(C12H16N3O3)(NCS)(C2H3N)]F000 = 852
Mr = 412.95Dx = 1.487 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3875 reflections
a = 12.507 (2) Åθ = 2.3–24.5º
b = 11.552 (1) ŵ = 1.32 mm−1
c = 12.787 (2) ÅT = 298 (2) K
β = 93.543 (1)ºBlock, blue
V = 1844.0 (4) Å30.23 × 0.21 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		4186 independent reflections
Radiation source: fine-focus sealed tube3143 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 298(2) Kθmax = 27.5º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→16
Tmin = 0.745, Tmax = 0.770k = −14→14
15401 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0462P)2 + 0.3686P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4186 reflectionsΔρmax = 0.31 e Å−3
229 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C12H16N3O3)(NCS)(C2H3N)]V = 1844.0 (4) Å3
Mr = 412.95Z = 4
Monoclinic, P21/nMo Kα
a = 12.507 (2) ŵ = 1.32 mm−1
b = 11.552 (1) ÅT = 298 (2) K
c = 12.787 (2) Å0.23 × 0.21 × 0.20 mm
β = 93.543 (1)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		4186 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3143 reflections with I > 2σ(I)
Tmin = 0.745, Tmax = 0.770Rint = 0.035
15401 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037229 parameters
wR(F2) = 0.098H-atom parameters constrained
S = 1.02Δρmax = 0.31 e Å−3
4186 reflectionsΔρmin = −0.25 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.21596 (2)0.93882 (2)0.25457 (2)0.04336 (11)
S10.26057 (7)0.83713 (8)−0.09663 (6)0.0811 (3)
O10.36548 (13)0.89111 (16)0.27255 (15)0.0596 (5)
O20.68408 (15)1.2638 (2)0.4508 (2)0.0856 (7)
O30.79311 (14)1.1489 (2)0.38151 (18)0.0819 (7)
N10.23620 (14)1.03387 (16)0.38324 (14)0.0414 (4)
N20.06710 (15)1.01357 (17)0.21204 (15)0.0452 (5)
N30.14008 (19)0.7828 (2)0.3335 (2)0.0679 (6)
N40.22514 (18)0.8813 (2)0.11039 (18)0.0656 (6)
N50.70235 (15)1.1749 (2)0.40349 (17)0.0544 (5)
C10.42878 (17)1.05305 (18)0.37335 (17)0.0387 (5)
C20.44268 (19)0.95528 (19)0.30748 (19)0.0448 (5)
C30.5498 (2)0.9310 (2)0.2819 (2)0.0561 (7)
H30.56300.86500.24310.067*
C40.63293 (19)1.0008 (2)0.31240 (19)0.0537 (6)
H40.70160.98380.29290.064*
C50.61515 (17)1.0982 (2)0.37302 (18)0.0437 (5)
C60.51490 (17)1.1218 (2)0.40523 (17)0.0414 (5)
H60.50491.18470.44900.050*
C70.32677 (18)1.07729 (19)0.41476 (18)0.0408 (5)
H70.32661.12970.46990.049*
C80.14448 (19)1.0635 (2)0.44447 (19)0.0508 (6)
H8A0.16901.11130.50350.061*
H8B0.11460.99300.47190.061*
C90.05886 (19)1.1266 (2)0.3807 (2)0.0532 (6)
H9A0.09081.19180.34630.064*
H9B0.00721.15700.42710.064*
C100.00110 (19)1.0514 (2)0.2987 (2)0.0545 (6)
H10A−0.02550.98310.33280.065*
H10B−0.06041.09370.26870.065*
C110.0905 (2)1.1145 (2)0.1461 (2)0.0619 (7)
H11A0.02471.15220.12340.093*
H11B0.12651.08900.08600.093*
H11C0.13561.16780.18600.093*
C12−0.0019 (2)0.9324 (2)0.1481 (2)0.0624 (7)
H12A−0.01360.86360.18790.094*
H12B0.03280.91240.08560.094*
H12C−0.06940.96870.12940.094*
C130.24112 (19)0.8638 (2)0.0250 (2)0.0520 (6)
C140.1136 (2)0.7100 (2)0.3835 (2)0.0528 (6)
C150.0798 (2)0.6164 (3)0.4485 (2)0.0713 (8)
H15A0.12410.61450.51250.107*
H15B0.08620.54440.41200.107*
H15C0.00650.62810.46410.107*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.04219 (18)0.04213 (18)0.04608 (18)−0.00245 (12)0.00523 (12)−0.00212 (12)
S10.1006 (6)0.0958 (6)0.0481 (4)0.0151 (5)0.0143 (4)0.0046 (4)
O10.0443 (10)0.0475 (10)0.0868 (13)0.0035 (8)0.0027 (9)−0.0201 (9)
O20.0455 (11)0.0814 (15)0.128 (2)−0.0016 (10)−0.0067 (11)−0.0378 (14)
O30.0350 (10)0.1144 (18)0.0968 (16)0.0000 (11)0.0085 (10)−0.0257 (14)
N10.0392 (10)0.0449 (11)0.0406 (10)0.0004 (8)0.0073 (8)0.0032 (8)
N20.0432 (11)0.0459 (11)0.0465 (11)−0.0023 (9)0.0029 (9)0.0004 (9)
N30.0707 (15)0.0561 (14)0.0764 (16)−0.0128 (12)0.0011 (12)0.0113 (13)
N40.0653 (15)0.0780 (16)0.0540 (14)0.0053 (13)0.0064 (11)−0.0135 (12)
N50.0352 (11)0.0694 (15)0.0578 (13)0.0048 (10)−0.0037 (9)−0.0001 (11)
C10.0388 (12)0.0389 (12)0.0383 (11)0.0053 (9)0.0010 (9)0.0066 (9)
C20.0447 (13)0.0403 (13)0.0493 (13)0.0073 (10)0.0010 (10)0.0019 (10)
C30.0479 (14)0.0573 (16)0.0632 (17)0.0129 (12)0.0046 (12)−0.0134 (13)
C40.0382 (13)0.0689 (17)0.0543 (15)0.0120 (12)0.0053 (11)0.0003 (13)
C50.0350 (12)0.0511 (13)0.0446 (13)0.0048 (10)−0.0016 (10)0.0060 (11)
C60.0385 (12)0.0442 (13)0.0410 (12)0.0080 (10)−0.0009 (9)0.0018 (10)
C70.0413 (12)0.0425 (13)0.0386 (12)0.0038 (10)0.0026 (9)0.0014 (9)
C80.0416 (13)0.0644 (16)0.0475 (13)−0.0065 (12)0.0121 (11)−0.0042 (12)
C90.0407 (13)0.0600 (16)0.0603 (15)0.0010 (12)0.0144 (11)−0.0095 (13)
C100.0370 (12)0.0663 (17)0.0607 (16)−0.0002 (11)0.0069 (11)−0.0048 (13)
C110.0709 (18)0.0526 (16)0.0627 (17)0.0043 (14)0.0085 (14)0.0101 (13)
C120.0526 (15)0.0692 (18)0.0637 (17)−0.0074 (13)−0.0101 (13)−0.0108 (14)
C130.0489 (14)0.0508 (15)0.0563 (16)0.0029 (11)0.0036 (12)0.0008 (12)
C140.0508 (14)0.0462 (14)0.0613 (16)−0.0044 (12)0.0015 (12)−0.0010 (13)
C150.079 (2)0.0554 (17)0.080 (2)−0.0118 (16)0.0143 (16)0.0121 (15)
Geometric parameters (Å, °) top
Cu1—O11.950 (2)C4—C51.391 (4)
Cu1—N41.970 (2)C4—H40.9300
Cu1—N11.981 (2)C5—C61.371 (3)
Cu1—N22.093 (2)C6—H60.9300
Cu1—N32.299 (2)C7—H70.9300
S1—C131.618 (3)C8—C91.495 (3)
O1—C21.276 (3)C8—H8A0.9700
O2—N51.220 (3)C8—H8B0.9700
O3—N51.224 (3)C9—C101.511 (3)
N1—C71.281 (3)C9—H9A0.9700
N1—C81.469 (3)C9—H9B0.9700
N2—C111.479 (3)C10—H10A0.9700
N2—C121.485 (3)C10—H10B0.9700
N2—C101.487 (3)C11—H11A0.9600
N3—C141.119 (3)C11—H11B0.9600
N4—C131.140 (3)C11—H11C0.9600
N5—C51.441 (3)C12—H12A0.9600
C1—C61.379 (3)C12—H12B0.9600
C1—C21.426 (3)C12—H12C0.9600
C1—C71.439 (3)C14—C151.443 (4)
C2—C31.427 (3)C15—H15A0.9600
C3—C41.354 (4)C15—H15B0.9600
C3—H30.9300C15—H15C0.9600
O1—Cu1—N484.49 (9)C1—C6—H6119.7
O1—Cu1—N189.22 (7)N1—C7—C1126.5 (2)
N4—Cu1—N1162.26 (9)N1—C7—H7116.7
O1—Cu1—N2168.09 (8)C1—C7—H7116.7
N4—Cu1—N289.91 (9)N1—C8—C9112.3 (2)
N1—Cu1—N293.04 (7)N1—C8—H8A109.1
O1—Cu1—N398.37 (8)C9—C8—H8A109.1
N4—Cu1—N3101.30 (10)N1—C8—H8B109.1
N1—Cu1—N396.01 (8)C9—C8—H8B109.1
N2—Cu1—N393.03 (8)H8A—C8—H8B107.9
C2—O1—Cu1125.21 (15)C8—C9—C10113.2 (2)
C7—N1—C8116.47 (19)C8—C9—H9A108.9
C7—N1—Cu1122.92 (15)C10—C9—H9A108.9
C8—N1—Cu1120.52 (15)C8—C9—H9B108.9
C11—N2—C12108.2 (2)C10—C9—H9B108.9
C11—N2—C10109.4 (2)H9A—C9—H9B107.8
C12—N2—C10105.38 (19)N2—C10—C9115.0 (2)
C11—N2—Cu1105.60 (15)N2—C10—H10A108.5
C12—N2—Cu1111.08 (16)C9—C10—H10A108.5
C10—N2—Cu1116.96 (15)N2—C10—H10B108.5
C14—N3—Cu1170.0 (2)C9—C10—H10B108.5
C13—N4—Cu1168.5 (3)H10A—C10—H10B107.5
O2—N5—O3121.7 (2)N2—C11—H11A109.5
O2—N5—C5119.4 (2)N2—C11—H11B109.5
O3—N5—C5118.9 (2)H11A—C11—H11B109.5
C6—C1—C2120.6 (2)N2—C11—H11C109.5
C6—C1—C7118.2 (2)H11A—C11—H11C109.5
C2—C1—C7121.0 (2)H11B—C11—H11C109.5
O1—C2—C1123.3 (2)N2—C12—H12A109.5
O1—C2—C3120.4 (2)N2—C12—H12B109.5
C1—C2—C3116.2 (2)H12A—C12—H12B109.5
C4—C3—C2122.1 (2)N2—C12—H12C109.5
C4—C3—H3118.9H12A—C12—H12C109.5
C2—C3—H3118.9H12B—C12—H12C109.5
C3—C4—C5119.7 (2)N4—C13—S1178.4 (3)
C3—C4—H4120.1N3—C14—C15179.7 (3)
C5—C4—H4120.1C14—C15—H15A109.5
C6—C5—C4120.6 (2)C14—C15—H15B109.5
C6—C5—N5119.2 (2)H15A—C15—H15B109.5
C4—C5—N5120.2 (2)C14—C15—H15C109.5
C5—C6—C1120.6 (2)H15A—C15—H15C109.5
C5—C6—H6119.7H15B—C15—H15C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···N40.962.432.969 (3)115
C10—H10B···O3i0.972.483.082 (3)120
Symmetry codes: (i) x−1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.950 (2)Cu1—N22.093 (2)
Cu1—N41.970 (2)Cu1—N32.299 (2)
Cu1—N11.981 (2)
O1—Cu1—N484.49 (9)N1—Cu1—N293.04 (7)
O1—Cu1—N189.22 (7)O1—Cu1—N398.37 (8)
N4—Cu1—N1162.26 (9)N4—Cu1—N3101.30 (10)
O1—Cu1—N2168.09 (8)N1—Cu1—N396.01 (8)
N4—Cu1—N289.91 (9)N2—Cu1—N393.03 (8)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12B···N40.962.432.969 (3)115
C10—H10B···O3i0.972.483.082 (3)120
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

Financial support from the Hunan Provincial Natural Sciences Foundation of China (No. 03JJY3019) and the Hunan Provincial Educational Ministry Foundation of China (No. 05 C627) is acknowledged.

references
References top

Bruker (2002). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Hu, Z.-Q., Li, W.-H., Ding, Y. & Wu, Y. (2005). Acta Cryst. E61, m2526–m2527.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Ye, L.-J. & You, Z. (2007). Acta Cryst. E63, m523–m525.